1-phenyl 5-oxotetrazolines

ABSTRACT

Novel 1-phenyl-5-oxo-2-tetrazolines of formula I ##STR1## in which R 1  is C 1  -C 8  alkyl, C 3  -C 6  alkenyl, C 3  -C 6  alkynyl, C 3  -C 6  cycloalkyl, C 5  -C 6  cycloalkenyl, C 1  -C 4  alkyl- or halo-substituted C 3  -C 6  cycloalkyl, C 1  -C 4  alkyl- or halo-substituted C 5  -C 6  cycloalkenyl, halo-, C 1  -C 4  alkoxy- or phenyl-substituted C 3  -C 6  alkenyl, halo-, C 1  -C 4  alkoxy- or phenyl-substituted C 3  -C 8  alkynyl, or C 1  -C 8  alkyl that is substituted by halogen, C 1  -C 4  alkoxy, C 1  -C 4  alkylthio, C 1  -C 4  alkoxycarbonyl, C 3  -C 6  cycloalkyl, phenyl, cyano, hydroxy, halophenyl, C 1  -C 4  alkylphenyl or by a heteroaromatic radical, 
     R 2  is C 1  -C 6  alkyl, C 2  -C 6  alkenyl, C 2  -C 6  alkynyl, C 3  -C 6  cycloalkyl, cyclopentenyl or cyclohexenyl, or is C 1  -C 6  alkyl that is substituted by halogen, by C 1  -C 4  alkoxy or by C 1  -C 4  alkylthio, each of R 3  and R 4 , independently of the other, is hydrogen, halogen, C 1  -C 4  alkyl, C 1  -C 4  haloalkyl, C 1  -C 4  alkoxy, C 1  -C 4  alkylthio, C 3  -C 6  cycloalkyl, C 2  -C 4  alkenyl, C 2  -C 4  alkynyl, C 2  -C 6  alkoxyalkyl, C 2  -C 6  alkylthioalkyl, C 1  -C 4  cyanoalkyl, phenyl-C 2  -C 4  alkenyl or phenyl-C 2  -C 4  alkynyl, or R 3  and R 4  together are a --CH═CH--CH═CH--, --CH 2  --CH═CH--, --(CH 2 ) 4  --, --(CH 2 ) 3  --, --O--CH 2  --O--, --O--CH 2  --CH.sub. 2 --O--, --CH 2  --O--CH 2  --, --(CH 2 ) 2  --CH═CH-- or --CH 2  --CH═CH--CH 2  -- bridge, each of which may be substituted by one or two C 1  -C 4  alkyl groups, and 
     R 5  is hydrogen or a --Z--R 6  group in which 
     R 6  is phenyl, naphthyl or pyridyl, or is phenyl, naphthyl or pyridyl each of which is substituted by one or two substituents from the group halogen, C 1  -C 4  alkyl, C 1  -C 4  alkoxy, C 1  -C 4  haloalkoxy, C 1  -C 4  haloalkyl, C 1  -C 4  alkylthio, C 1  -C 4  haloalkylthio, di-C 1  -C 4  alkylamino, nitro, cyano, C 1  -C 4  alkoxycarbonyl and C 1  -C 4  alkylcarbonyl, and 
     Z is oxygen, sulfur, a direct bond, --NH--, --N(C 1  -C 2  alkyl)--, --N(CHO)--, --CH 2  --, --CH(CH 3 )-- or --C(CH 3 ) 2  -- 
     can be used as pesticides. Preferably, insects and arachnids can be controlled.

This is a divisional of Ser. No. 539,755 filed Jun. 18, 1990, now, U.S.Pat. No. 5,066,667.

The present invention relates to novel substituted1-phenyl-5-thioxo-2-tetrazolines, to processes and intermediates for thepreparation thereof, to pesticidal compositions containing thosecompounds, and to the use thereof in the control of pests.

The 1-phenyl-5-thioxo-2-tetrazolines according to the inventioncorrespond to formula I ##STR2## in which R¹ is C₁ -C₈ alkyl, C₃ -C₆alkenyl, C₃ -C₆ alkynyl, C₃ -C₆ cycloalkyl, C₅ -C₆ cycloalkenyl, C₁ -C₄alkyl- or halo-substituted C₃ -C₆ cycloalkyl, C₁ -C₄ alkyl-orhalo-substituted C₅ -C₆ cycloalkenyl, halo-, C₁ -C₄ alkoxy- orphenyl-substituted C₃ -C₆ alkenyl, halo-, C₁ -C₄ alkoxy- orphenyl-substituted C₃ -C₈ alkynyl, or C₁ -C₈ alkyl that is substitutedby halogen, C₁ -C₄ alkoxy, C₁ -C₄ alkylthio, C₁ -C₄ alkoxycarbonyl, C₃-C₆ cycloalkyl, phenyl, cyano, hydroxy, halophenyl, C₁ -C₄ alkylphenylor by a heteroaromatic radical,

R² is C₁ -C₆ alkyl, C₂ -C₆ alkenyl, C₂ -C₆ alkynyl,

C₃ -C₆ cycloalkyl, cyclopentenyl or cyclohexenyl, or is C₁ -C₆ alkylthat is substituted by halogen, by C₁ -C₄ alkoxy or by C₁ -C₄ alkylthio,

each of R³ and R⁴, independently of the other, is hydrogen, halogen, C₁-C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ alkoxy, C₁ -C₄ alkylthio, C₃ -C₆cycloalkyl, C₂ -C₄ alkenyl, C₂ -C₄ alkynyl, C₂ -C₆ alkoxyalkyl, C₂ -C₆alkylthioalkyl, C₁ -C₄ cyanoalkyl, phenyl-C₂ -C₄ alkenyl or phenyl-C₂-C₄ alkynyl, or R³ and R⁴ together are a --CH═CH--CH═CH--, --CH₂--CH═CH--, --(CH₂)₄ --, --(CH₂)₃ --, --O--CH₂ --O--, --O--CH₂ --CH₂--O--, --CH₂ --O--CH₂ --, --(CH₂)₂ --CH═CH-- or --CH₂ --CH═CH--CH₂ --bridge, each of which may be substituted by one or two C₁ -C₄ alkylgroups, and

R⁵ is hydrogen or a --Z--R⁶ group in which

R⁶ is phenyl, naphthyl or pyridyl, or is phenyl, naphthyl or pyridyleach of which is substituted by one or two substituents from the grouphalogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₁ -C₄ haloalkoxy, C₁ -C₄haloalkyl, C₁ -C₄ alkylthio, C₁ -C₄ haloalkylthio, di-C₁ -C₄ alkylamino,nitro, cyano, C₁ -C₄ alkoxycarbonyl and C₁ -C₄ alkylcarbonyl, and

Z is oxygen, sulfur, a direct bond, --NH--, --N(C₁ -C₂ alkyl)--,--N(CHO)--, --CH₂ --, --CH(CH₃)-- or --C(CH₃)₂ --.

As a class, 1-phenyl-5-oxo- or -5-thioxo-2-tetrazolines are known fromthe literature to be herbicidally active or as auxiliaries forphotographic materials. Compounds of the type mentioned are disclosed,for example, in DE-OS 1 447 662, DD-PS 119 322 and WO 85/01939.

The individual generic terms used in the definition of formula Iaccording to the invention are to be understood as follows: The halogenatoms suitable as substituents are both fluorine and chlorine atoms aswell as bromine and iodine atoms, with fluorine and chlorine beingpreferred. Halogen in such cases is either an independent substituent orpart of a substituent as in haloalkyl, haloalkoxy, haloalkylthio orhalophenyl.

The alkyl, alkylthio and alkoxy radicals suitable as substituents may bestraight-chain or branched. There may be mentioned as examples of suchalkyl radicals methyl, ethyl, propyl, isopropyl, butyl, i-butyl,sec.-butyl, tert.-butyl or pentyl, hexyl, octyl and their isomers.Suitable alkoxy radicals are, for example: methoxy, ethoxy, propoxy,isopropoxy or butoxy and their isomers. Alkylthio is, for example,methylthio, ethylthio, isopropylthio, propylthio or the isomers ofbutylthio. Substituents that are composed of several generic groups,such as alkoxyalkyl or alkylthioalkyl, contain appropriate combinationsof the mentioned individual substituents.

The alkenyl and alkynyl radicals suitable as substituents may bestraight-chain or branched and contain one or more unsaturated bonds. Itis also possible for doubly and triply unsaturated bonds to be presentin the same radical. These unsaturated radicals preferably contain fromtwo to six carbon atoms. Examples of such alkenyl and alkynyl radicalsare, inter alia, vinyl, allyl, 1-propenyl, isopropenyl, allenyl,butenyls, butadienyls, hexenyls, hexanedienyl, ethynyl, 1-propynyl,2-propynyl, butinyls, pentynyls, hexynyls, hexadiynyls and2-penten-4-ynyl.

The phenylalkyl, phenylalkenyl and phenylalkynyl radicals suitable assubstituents may be straight-chain or branched. The following, interalia, are suitable examples: benzyl, phenethyl, phenylpropyl,phenylisopropyl, phenylbutyl and its isomers, phenylvinyl, phenylallyl,phenylbutenyl, phenylethynyl, phenylpropynyl and phenylbutynyl.

If the alkyl, alkoxy, alkylthio, alkenyl, alkynyl or phenylalkylradicals suitable as substituents are halo-substituted, then they may beonly partially halogenated or alternatively perhalogenated. Thehalosubstitution of the phenylalkyl radicals may be either in the phenylnucleus or in the alkyl chain, or in both simultaneously. The abovedefinitions for the halogen atoms, alkyl, alkoxy, alkylthio, alkenyl,alkynyl and phenylalkyl groups apply here too. Examples of the alkylelements of these groups are: methyl mono- to tri-substituted byfluorine, chlorine and/or bromine, such as, for example, CHF₂ or CF₃ ;ethyl mono- to penta-substituted by fluorine, chlorine and/or bromine,such as, for example, CH₂ CF₃, CF₂ CF₃, CF₂ CCl₃, CF₂ CHCl₂, CF₂ CHF₂,CF₂ CFCl₂, CF₂ CHBr₂, CF₂ CHClF, CF₂ CHBrF or CClFCHClF; propyl orisopropyl each mono- to hepta-substituted by fluorine, chlorine and/orbromine, such as, for example, CH₂ CHBrCH₂ Br, CF₂ CHFCF₃, CH₂ CF₂ CF₃or CH(CF₃)₂ ; butyl or an isomer thereof each mono- to nona-substitutedby fluorine, chlorine and/or bromine, such as, for example,CF(CF₃)CHFCF₃ or CH₂ (CF₂)₂ CF₃ ; vinyl, propynyl or pentadiynyl eachmono- to tri-substituted by fluorine, chlorine and/or bromine; allyl,1-propenyl, butadienyl or a butynyl radical each mono- topenta-substituted by fluorine, chlorine and/or bromine,; a butenyl,pentadienyl or pentynyl radical each mono- to hepta-substituted byfluorine, chlorine and/or bromine; benzyl mono- to hepta-substituted byfluorine, chlorine and/or bromine; phenethyl mono-to nona-substituted byfluorine, chlorine and/or bromine; phenylpropyl or phenylisopropyl eachmono- to undecasubstituted by fluorine, chlorine and/or bromine.

Cycloalkyl radicals suitable as substituents are, for example,cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

Examples of alkoxycarbonyl and alkylcarbonyl radicals aremethoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl andbutoxycarbonyl. Alkylcarbonyl is, for example, acetyl, propionyl,butyryl or valeryl, or an isomer thereof.

Alkylphenyl is a phenyl group substituted by an alkyl group. Aheteroaromatic radical in the definition of R¹ is to be understood as anaromatic ring that contains one or more hetero atoms as ring members.The following are examples: pyrrole, pyrazole, imidazole, triazoles,tetrazole, oxazoles, thiazoles, oxadiazoles, thiadiazoles, pyridine,pyrimidine, pyrazine, pyridazine, triazines and quinoline.

In the case where, as in the definition of R¹, certain radicals maythemselves be further substituted, then those radicals contain one ormore substituents, but preferably no more than two.

In the case where R³ and R⁴ together form one of the mentioned bridges,R³ and R⁴ are bonded to adjacent carbon atoms of the phenyl ring.

Among the compounds of formula I, attention is drawn to those subgroupsin which

a) R¹ is C₁ -C₅ alkyl, C₃ -C₅ alkenyl, C₃ -C₅ alkynyl, C₅ -C₆cycloalkyl, or C₁ -C₄ alkyl that is substituted by C₁ -C₄ alkoxy, byphenyl or by cyclopropyl, or

b) R² is C₁ -C₄ alkyl or C₅ -C₆ cycloalkyl, or

c) each of R³ and R⁴, independently of the other, is hydrogen, C₁ -C₄-alkyl, C₂ -C₃ alkynyl, C₂ -alkenyl, or C₂ -C₄ alkoxyalkyl, or

d) R⁵ is hydrogen, benzyl, 1-phenethyl, phenoxy, halophenoxy,phenylthio, phenyl, dichloropyridyloxy, N-formylanilinyl orN-formylhaloanilinyl.

Of the compounds of sub-group c), attention is drawn to those in whichone of the substituents R³ and R⁴ is hydrogen and the other occupies the6-position of the phenyl ring, especially those in which R³ is C₁ -C₄alkyl in the 6-position of the phenyl ring and R⁴ is hydrogen.

Preferred compounds of sub-group d) are those in which R⁵ is hydrogen,benzyl, phenoxy or halophenoxy in the 4-position of the phenyl ring.

Groups of compounds of formula I that have proved to be especiallypreferred are those compounds in which R² is C₁ -C₄ alkyl or C₅ -C₆cycloalkyl, R³ is C₁ -C₄ alkyl in the 6-position of the phenyl ring, R⁴is hydrogen and R⁵ is hydrogen, benzyl, phenoxy or halophenoxy in the4-position of the phenyl ring.

Also preferred are compounds of formula I in which R¹ is C₁ -C₅ alkyl,C₃ -C₅ alkenyl, C₃ -C₅ alkynyl, C₅ -C₆ cycloalkyl, or C₁ -C₄ alkyl thatis substituted by C₁ -C₄ alkoxy, by phenyl or by cyclopropyl, R² is C₁-C₄ alkyl or C₅ -C₆ cycloalkyl, each of R³ and R⁴, independently of theother, is hydrogen, C₁ -C₄ alkyl, C₂ -C₃ alkynyl, C₂ -C₃ alkenyl or C₂-C₄ alkoxyalkyl and R⁵ is hydrogen, benzyl, 1-phenethyl, phenoxy,halophenoxy, phenylthio, phenyl, dichloropyridyloxy, N-formylanilinyl orN-formylhaloanilinyl.

A most especially outstanding group of compounds of formula I is that inwhich R¹ is C₁ -C₅ alkyl or C₅ -C₆ cycloalkyl, R² is C₁ -C₄ alkyl or C₅-C₆ cycloalkyl, R³ is C₁ -C₄ alkyl in the 6-position of the phenyl ring,R⁴ is hydrogen, and R⁵ is hydrogen, benzyl, phenoxy or halophenoxy inthe 4-position of the phenyl ring.

The following may be mentioned as preferred individual compounds offormula I:

1-(2-ethyl-6-isopropylphenyl)-4-isopropyl-5-thioxo-2-tetrazoline,

1-(2,6-diisopropyl-4-phenoxyphenyl)-4-isopropyl-5-thioxo-2-tetrazoline,

1-(2-ethyl-6-isopropylphenyl)-4-methyl-5-thioxo-2-tetrazoline,

1-(2,6-diisopropyl-4-phenoxyphenyl)-4-(2,2-dimethylpropyl)-5-thioxo-2-tetrazoline,

1-(2-cyclopentyl-6-isopropylphenyl)-4-isopropyl-5-thioxo-2-tetrazoline,

1-(2-cyclopentyl-6-isopropylphenyl)-4-sec.-butyl-5-thioxo-2-tetrazoline,

1-(2,6-diisopropyl-4-phenoxyphenyl)-4-ethyl-5-thioxo-2-tetrazoline,

1-(2,6-diisopropylphenyl)-4-(1-methyl-2-methoxyethyl)-5-thioxo-2-tetrazoline,

1-(2-methyl-6-isopropylphenyl)-4-isopropyl-5-thioxo-2-tetrazoline,

1-(2-methyl-6-isopropylphenyl)-4-(2,2-dimethylpropyl)-5-thioxo-2-tetrazoline,

1-(2,6-diisopropyl-4-phenoxyphenyl)-4-cyclopentyl-5-thioxo-2-tetrazoline,

1-(2,6-diisopropylphenyl)-4-isopropyl-5-thioxo-2-tetrazoline,

1-(2-ethyl-6-isopropylphenyl)-4-(2,2-dimethylpropyl)-5-thioxo-2-tetrazoline

1-(2,6-diisopropylphenyl)-4-(2,2-dimethylpropyl)-5-thioxo-2-tetrazoline,

1-(2,6-diisopropylphenyl)-4-(2-cyclohexenyl)-5-thioxo-2-tetrazoline,

1-(2-methyl-6-isopropylphenyl)-4-sec.-butyl-5-thioxo-2-tetrazoline,

1-(2,6-diisopropyl-4-phenoxyphenyl)-4-cyclopropylmethyl-5-thioxo-2-tetrazoline,

1-(2,6-diisopropyl-4-benzylphenyl)-4-sec.-butyl-5-thioxo-2-tetrazoline,

1-(2,6-diisopropyl-4-benzylphenyl)-4-(2,2-dimethylpropyl)-5-thioxo-2-tetrazoline,

1-(2,6-diisopropyl-4-benzylphenyl)-4-isopropyl-5-thioxo-2-tetrazoline,

1-[2,6-diisopropyl-4-(2-fluorophenoxy)-phenyl]-4-isopropyl-5-thioxo-2-tetrazoline,

1-[2,6-diisopropyl-4-(1-phenethyl)-phenyl]-4-isopropyl-5-thioxo-2-tetrazoline,

1-(2-cyclopentyl-6-isopropyl-4-phenoxyphenyl)-4-isopropyl-5-thioxo-2-tetrazoline,

1-(2-tert.-butyl-6-methylphenyl)-4-isopropyl-5-thioxo-2-tetrazoline,

1-(2-tert.-butyl-6-methylphenyl)-4-sec.-butyl-5-thioxo-2-tetrazoline,

1-(2-tert.-butyl-6-methylphenyl)-4-(2,2-dimethylpropyl)-5-thioxo-2-tetrazolineand

1-(2,6-diethylphenyl)-4-isopropyl-5-thioxo-2-tetrazoline.

The compounds of formula I of the invention can be prepared according toprocesses that are known in principle, for example by

a) treating a 1-phenyl-5-oxo-2-tetrazoline of formula II ##STR3## inwhich R¹, R², R³, R⁴ and R⁵ are as defined for formula I, with athionating agent, or

b) alkylating a 1-phenyl-5-thioxo-2-tetrazoline of formula III ##STR4##in which R², R³, R⁴ and R⁵ are as defined for formula I, with analkylating agent of formula IV

    X--R.sup.11                                                (IV)

in which R¹¹ has the same meaning as R¹ in formula I or is a substituentthat can be converted into R¹, and X is a leaving group, and convertingthe resulting 1-phenyl-5-mercaptotetrazole of formula V ##STR5## bymeans of a rearrangement reaction into the corresponding1-phenyl-5-thioxo-2-tetrazoline of formula Ia ##STR6## and, ifappropriate, converting the substituent R¹¹ into a radical according tothe definition of R¹, or

c) alkylating a 1-phenyl-5-thioxo-2-tetrazoline of formula III in thepresence of a base by reaction with an activated carbonylvinyl orcyanovinyl derivative that can be converted into the radical R¹ and, ifdesired, converting the introduced substituent into a radical accordingto the definition of R¹.

The reaction of variant a) converts the carbonyl function of thestarting material of formula II directly into a thiocarbonyl function.Analogous thionation reactions are known in the literature. Analogousprocesses are described, for example, in Chem. Ber. 118, 526 (1985) andJ. Org. Chem. 41, 1875 (1976). Process a) according to the invention ispreferably carried out in the presence of an inert organic solvent.Suitable solvents are aromatic solvents, such as benzene, toluene,xylene, mesitylene, chlorobenzene, dichlorobenzene, pyridine ortetraline; chlorinated hydrocarbons, such as methylene chloride,chloroform, carbon tetrachloride, ethylene chloride, trichloroethane ortetrachloroethane; nitriles, such as acetonitrile or propionitrile orethers such as dioxan, tetrahydrofuran or dimethylethylene glycol. Thereaction temperatures are generally from +20° C. to +200° C. A range offrom +60° C. to +140° C. is preferred, and attention must be drawnespecially to the boiling range of the reaction mixture. The reactionaccording to the invention is also promoted by performing the thionationreaction using ultrasound and employing a temperature of from +20° C. tothe boiling point of the mixture. The use of ultrasound sources topromote thionation reactions is described in analogous processes in J.Org. Chem. 46, 3558 (1981).

Numerous thionation agents have already been described in theliterature. Most of these agents can be used in the processes accordingto the invention. Reagents that have proved especially favourable areO,O-diethyldithiophosphoric acid (C₂ H₅ O)₂ PS₂ H, boron sulfide B₂ S₃or B₂ S₅, phosphorus pentasulfide P₂ S₅ or2,4-bis-(4-methoxyphenyl)-1,3-dithia-2,4-diphosphetane-2,4-disulfide(Lawesson's reagent).

The reaction of variant b) of the process of the invention can either beperformed in two reaction steps with isolation of the intermediate offormula V, or carried out in a single process step without isolation ofthe intermediate. The rearrangement reaction of V to form Ia can beeffected either thermally by heating, or in the presence of a suitablecatalyst. Suitable rearrangement catalysts are generally complexcompounds of transition metals, especially palladium complexes, such as,for example, bis-benzonitrilo-palladium chloride of the formula Pd(C₆ H₅--CN)₂ Cl₂. Process variant b) according to the invention isadvantageously carried out in the presence of an inert organic solventat the boiling temperature of the reaction mixture. Suitable solventsare amides, such as dimethylformamide or diethylformamide, aromaticsolvents, such as benzene, toluene, xylene, mesitylene, chlorobenzene,dichlorobenzene, pyridine or tetraline; chlorinated hydrocarbons, suchas methylene chloride, chloroform, carbon tetrachloride, ethylenechloride, trichloroethane or tetrachloroethane; nitriles, such asacetonitrile or propionitrile, or ethers, such as dioxan,tetrahydrofuran or dimethylethylene glycol.

The leaving groups X are selected from the series of leaving groupscustomary for nucleophilic substitution reactions. Suitable leavinggroups X are preferably chlorine, bromine, iodine, toluenesulfonyloxy,methanesulfonyloxy, trifluoromethanesulfonyloxy and benzenesulfonyloxy.Substituents of the definition R¹¹ that can be converted into radicalsof the definition R¹ are those radicals that can be thus converted bysimple reactions, such as, for example, hydrolysis, hydrogenation oraddition reactions. Examples are carbonyl group-containing radicals thatare halogenated, hydrogenated or hydrolysed after the substitution, orunsaturated substituents that, for example, are converted into saturatedderivatives by 1,2-addition, such as by halogen, hydrogen halide oralcohol addition.

In process variant c), there are linked with the intermediate of formulaIII by 1,4-addition those radicals R¹ that contain at least 3 carbonatoms and can be formed under the conditions of a Michael addition. Thestructural elements carbonylvinyl ##STR7## must be present as activatedMichael reagents in the alkylating agents. If desired, the resultingproducts can be converted by conventional derivatisation reactions intodifferent radicals R¹. Suitable bases for carrying out variant c) arepreferably tert.-amines, such as triethylamine, pyridine ordimethylaminopyridine, but also alkali metal alcoholates or alkali metalhydrides. Advantageously process c) is carried out in an inert solventat the boiling temperature of the reaction mixture. Such solvents arealcohols, such as methanol, ethanol, propanol or isopropanol, amides,such as dimethylformamide or diethylformamide, aromatic solvents, suchas benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene,pyridine or tetraline; chlorinated hydrocarbons, such as methylenechloride, chloroform, carbon tetrachloride, ethylene chloride,trichloroethane or tetrachloroethane; nitriles, such as acetonitrile orpropionitrile, or ethers, such as dioxan, tetrahydrofuran ordimethylethylene glycol.

In principle it is also possible in the preparation of compounds offormula I to convert the substituents R¹, R², R³, R⁴ and R⁵ by suitablederivatisation reactions or substitution reactions into differentradicals within the corresponding definition. For example, a halogensubstituent included under R³ or R⁴ can be replaced by a --Z--R⁶ radicalby a nucleophilic substitution reaction.

The starting materials of formula IV are known and can be obtainedcommercially, or they can be obtained according to processes that areknown per se.

The starting compounds of formula II can be obtained according to thefollowing Scheme 1 from known anilines of formula VI by way ofisocyanates of formula VII and 1-phenyl-5-oxotetrazolines of formulaVIII. ##STR8## R², R³, R⁴ and R⁵ are as defined for formula I and X andR¹¹ are as defined for formula IV.

The starting compounds of formula III can be obtained according toScheme 2 from known anilines of formula VI by way of thioisocyanates offormula IX or anilinocarbodithioates of formula X. ##STR9##

R², R³, R⁴ and R⁵ are as defined for formula I.

The intermediates of formula III can be obtained from those of formulaII also by treatment with thionating agents, such as those used forvariant a) of the preparation process according to the invention.

The intermediates of formulae II and VIII are novel. They were developedspecifically for the synthesis of compounds of formula I and the presentinvention therefore extends to them.

It has been found that whilst being well tolerated by warm-bloodedanimals and plants, the compounds of formula I of the invention arevaluable active ingredients in the control of pests. In particular, theuse of the active ingredients of the invention is directed to insectsand spinning organisms that occur in useful plants and ornamentals inagriculture, especially in cotton, vegetable and fruit plantations, inforestry, in stock and material protection and also in the hygienesector especially in connection with domestic animals and productivelivestock. They are effective against all or individual stages ofdevelopment of normally sensitive species and also resistant species.Their effect may manifest itself in a direct kill of the pests, or notuntil after some time, for example during shedding, or in a reducedoviposition and/or hatching rate. The following are included among theabove-mentioned pests: of the order Lepidoptera, for example Amyloisspp., Coleophora spp., Yponomeuta spp., Prays spp., Lyonetia spp.,Keiferia lycopersicella, Pectinophora gossypiella, Plutella xylostella,Leucoptera scitella, Lithocollethis spp., Aegeria spp., Synanthedonspp., Adoxophyes spp., Pieris spp., Archips spp., Argyrotaenia spp.,Choristoneura spp., Pandemis spp., Sparganothis spp., Cnephasia spp.,Acleris spp., Tortrix spp., Cochylis spp., Eupoecilia ambiguella, Hedyanubiferana, Lobesia botrana, Eucosma spp., Cydia spp., Grapholita spp.,Pammene spp., Malacosoma spp., Manduca sexta, Chilo spp., Diatraea spp.,Crocidolomia binotalis, Ostrinia nubilalis, Cadra cautella, Ephestiaspp., Operophtera spp., Thaumetopoea spp., Euproctis spp., Lymantriaspp., Agrotis spp., Euxoa spp., Mamestra brassicae, Panolis flammea,Busseola fusca, Sesamia spp., Spodoptera spp., Heliothis spp., Eariasspp., Autographa spp., Trichoplusia ni, Cryptophlebia leucotreta,Phthorimaea operculella, Diparopsis castanea, Alabama argillaceae,Anticarsia gemmatalis and Hellula undalis, Cnaphalocrocis spp.,Scirpophaga spp., Hyphantria cunea, Carposina nipponensis, Phtorimaeaoperculella, Cryptophlebia leucotreta, Clysia ambiguella and Pierisrapae; of the order Coleoptera, for example Sitotroga spp., Leptinotarsadecemlineata, Diabrotica spp., Agriotes spp., Anthonomus spp.,Cosmopolites spp., Dermestes spp., Epilachna spp., Orycaephilus spp.,Sitophilus spp., Otierhynchus spp., Tribolium spp., Tenebrio spp.,Melolontha spp., Popillia spp., Rhizopertha spp., Trogoderma spp.,Curculio spp., Eremnus spp. and Phlyctinus spp., Lissorhoptrus spp.,Chaetocnema tibialis, Psylliodes spp., Atomaria linearis andScarabeidae; of the order Orthoptera, for example Blatta spp.,Periplaneta spp., Leucophaea maderae, Blattella spp., Gryllotalpa spp.,Locusta spp. and Schistocerca spp.; of the order Isoptera, for exampleReticulitermes spp.; of the order Psocoptera, for example Liposcelisspp.; of the order Anoplura, for example Phylloxera spp., Pemphigusspp., Pediculus spp., Haematopinus spp. and Linognathus spp., of theorder Mallophaga, for example Trichodectes spp. and Damalinea spp.; ofthe order Thysanoptera, for example Hercinothrips spp., Thrips tabaci,Taeniothrips spp. and Scirtothrips aurantii, Frank Liniella spp. andThrips palmi; of the order Heteroptera, for example Eurygaster spp.,Dysdercus spp., Piesma spp., Cimex spp., Rhodnius spp., Triatoma spp.,Nezzara spp., Scotinophara spp., Leptocorisa spp., Euchistus spp.,Sahlbergella singularis and Distantiella theobroma; of the orderHomoptera, for example Aleurodes brassicae, Bemisia tabaci, Trialeurodesvaporariorum, Aphididae, Empoasca spp., Nephotettix spp., Laodelphaxspp., Nilaparvata spp., Aonidiella spp., Lecanium corni, Saissetia spp.,Aspidiotus spp., Pseudococcus spp., Planococcus spp., Pseudaulacaspisspp., Quadraspidiotus spp., Psylla spp., Chrysomphalus aonidium,Aleurothrixus floccosus, Trioza erytreae, Eriosoma larigerum, Unaspiscitri, Ceroplaster spp. and Partatoria spp., Lepidosaphes spp.,Erythroneura spp., Gascardia spp., Coccus hesperidum, Pulvinariaaethiopica, Schizaphis spp., Aphis spp., Sitobion spp., Macrosiphusspp., Rhopalosiphum spp., Myzus spp., Pemphigus spp., Scaphoideus spp.and Chrysophalus dictyospermi; of the order Hymenoptera, for exampleDiprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespaspp., Neodiprion spp. and Solenopsis spp., Atta spp., Acromyrex,Diprionidae, Gilpinia polytoma and Cephus spp.; of the order Diptera,for example Aedes spp., Culex spp., Drosophila melanogaster, Musca spp.,Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp.,Cuterebra spp., Glossina spp., Gastrophilus spp., Hyppobosca spp.,Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp.,Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami,Ceratitis spp., Dacus spp., Tipula spp., Liriomyza spp., Melanagromyzaspp., Antherigona soccata, Sciara spp., Rhagoletis pomonella andOrseolina spp.; of the order Siphonaptera, for example Xenopsyllacheopis and Ceratophyllus spp.; of the order Acarina, for examplePanonychus spp., Tetranychus spp., Tarsonemus spp., Bryobia praetiosa,Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae,Eriophyes spp., Phyllocoptruta oleivora, Boophilus spp., Rhipicephalusspp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp.,Chorioptes spp., Saracoptes spp., Aceria sheldoni, Polyphagotarsonemuslatus, Eotetranychus carpini and Brevipalpus spp., Calipitrimerus spp.,Aculus schlechtendali, Rhizoglyphus spp. and Olygonychus pratensis andof the order Thysanura, for example Lepisma saccharina.

The good pesticidal activity of the compounds of formula I of theinvention corresponds to a death rate (mortality) of at least 50-60% ofthe pests mentioned.

The activity of the compounds of the invention and of the compositionscontaining them can be substantially broadened and adapted to theprevailing circumstances by the addition of other insecticides and/oracaricides. Examples of suitable additives are representatives of thefollowing classes of active substances: organophosphorus compounds,nitrophenols and derivatives thereof, formamidines, ureas, carbamates,pyrethroids, chlorinated hydrocarbons and Bacillus thuringiensispreparations.

The compounds of formula I are used in unmodified form or, preferably,together with the adjuvants conventionally employed in the art offormulation, and can therefore be formulated in known manner e.g. intoemulsifiable concentrates, directly sprayable or dilutable solutions,dilute emulsions, wettable powders, soluble powders, dusts, granulates,and also encapsulations in polymer substances. As with the nature of thecompositions, the methods of application, such as spraying, atomising,dusting, scattering or pouring, are chosen in accordance with theintended objectives and the prevailing circumstances.

The formulations, i.e. the compositions, preparations or mixturescontaining the compound (active ingredient) of formula I or combinationsof those compounds with other insecticides or acaricides and, ifdesired, a solid or liquid adjuvant, are prepared in known manner, e.g.by homogeneously mixing and/or grinding the active ingredients withextenders, e.g. solvents, solid carriers and, where appropriate,surface-active compounds (surfactants).

Suitable solvents are: aromatic hydrocarbons, preferably the fractionscontaining 8 to 12 carbon atoms, e.g. xylene mixtures or substitutednaphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate,aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols andglycols and their ethers and esters, such as ethanol, ethylene glycol,ethylene glycol monomethyl or monoethyl ether, ketones such ascyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone,dimethyl sulfoxide or dimethylformamide, as well as vegetable oils orepoxidised vegetable oils, such as epoxidised coconut oil or soybeanoil; or water.

The solid carriers used e.g. for dusts and dispersible powders arenormally natural mineral fillers such as calcite, talcum, kaolin,montmorillonite or attapulgite. In order to improve the physicalproperties it is also possible to add highly dispersed silicic acids orhighly dispersed absorbent polymers. Suitable granulated adsorptivecarriers are porous types, for example pumice, broken brick, sepioliteor bentonite; and suitable nonsorbent carriers are calcite or sand. Inaddition, a great number of granulated materials of inorganic or organicnature can be used, e.g. especially dolomite or pulverised plantresidues.

Depending on the nature of the compound of formula I to be formulated orof the combinations of those compounds with other insecticides oracaricides, suitable surface-active compounds are non-ionic, cationicand/or anionic surfactants having good emulsifying, dispersing andwetting properties. The term "surfactants" will also be understood ascomprising mixtures of surfactants.

Both so-called water-soluble soaps and also water-soluble syntheticsurface-active compounds are suitable anionic surfactants.

Suitable soaps are the alkali metal salts, alkaline earth metal salts orunsubstituted or substituted ammonium salts of higher fatty acids (C₁₀-C₂₂), e.g. the sodium or potassium salts of oleic or stearic acid, orof natural fatty acid mixtures which can be obtained e.g. from coconutoil or tall oil. Mention may also be made of fatty acid methyltaurinsalts and modified and unmodified phospholipids.

More frequently, however, so-called synthetic surfactants are used,especially fatty sulfonates, fatty sulfates, sulfonated benzimidazolederivatives or alkylarylsulfonates.

The fatty sulfonates or sulfates are usually in the form of alkali metalsalts, alkaline earth metal salts or unsubstituted or substitutedammonium salts and generally contain a C₈ -C₂₂ alkyl radical which alsoincludes the alkyl moiety of acyl radicals, e.g. the sodium or calciumsalt of lignosulfonic acid, of dodecylsulfate or of a mixture of fattyalcohol sulfates obtained from natural fatty acids. These compounds alsocomprise the salts of sulfated and sulfonated fatty alcohol/ethyleneoxide adducts. The sulfonated benzimidazole derivatives preferablycontain 2 sulfonic acid groups and one fatty acid radical containingapproximately 8 to 22 carbon atoms. Examples of alkylarylsulfonates arethe sodium, calcium or triethanolamine salts of dodecylbenzenesulfonicacid, dibutylnaphthalenesulfonic acid, or of a condensate ofnaphthalenesulfonic acid and formaldehyde. Also suitable arecorresponding phosphates, e.g. salts of the phosphoric acid ester of anadduct of p-nonylphenol with 4 to 14 moles of ethylene oxide.

Non-ionic surfactants are preferably polyglycol ether derivatives ofaliphatic or cycloaliphatic alcohols, saturated or unsaturated fattyacids and alkylphenols, said derivatives containing 3 to 30 glycol ethergroups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moietyand 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.Further suitable non-ionic surfactants are the water-soluble adducts ofpolyethylene oxide with polypropylene glycol,ethylenediaminopolypropylene glycol and alkylpolypropylene glycolcontaining 1 to 10 carbon atoms in the alkyl chain, which adductscontain 20 to 250 ethylene glycol ether groups and 10 to 100 propyleneglycol ether groups. These compounds usually contain 1 to 5 ethyleneglycol units per propylene glycol unit.

Examples of non-ionic surfactants are nonylphenolpolyethoxyethanols,castor oil polyglycol ethers, castor oil thioxilate,polypropylene/polyethylene oxide adducts,tributylphenoxypolyethoxyethanol, polyethylene glycol andoctylphenoxypolyethoxyethanol. Fatty acid esters of polyoxyethylenesorbitan, e.g. polyoxyethylene sorbitan trioleate, are also suitablenon-ionic surfactants.

Cationic surfactants are preferably quaternary ammonium salts whichcontain, as N-substituent, at least one C₈ -C₂₂ alkyl radical and, asfurther substituents, unsubstituted or halogenated lower alkyl, benzylor hydroxy-lower alkyl radicals. The salts are preferably in the form ofhalides, methylsulfates or ethylsulfates, e.g. stearyltrimethylammoniumchloride or benzyl-di-(2-chloroethyl)-ethylammonium bromide.

The surfactants customarily used in the art of formulation aredescribed, inter alia, in the following publications:

"1985 International Mc Cutcheon's Emulsifiers & Detergents", Glen RockNJ USA, 1985",

H. Stache, "Tensid-Taschenbuch", 2nd edition, C. Hanser Verlag Munich,Vienna 1981,

M. and J. Ash "Encyclopedia of Surfactants", vol. I-III, ChemicalPublishing Co., New York, 1980-1981.

The pesticidal compositions usually contain 0.1 to 99%, especially 0.1to 95%, of a compound of formula I or combinations of that compound withother insecticides or acaricides, 1 to 99.9% of a solid or liquidadjuvant and 0 to 25%, preferably 0.1 to 20%, of a surfactant. Whereascommerical products will preferably be formulated as concentrates, theend user will normally employ dilute formulations that containsubstantially lower concentrations of active ingredient. Typicalconcentrations are from 0.1 to 1000 ppm, preferably from 0.1 to 500 ppm.The rate of application per hectare is generally from 1 to 1000 g ofactive ingredient per hectare, preferably from 25 to 500 g/ha.

The preferred formulations are composed especially as follows:(throughout percentages are by weight)

    ______________________________________                                        Emulsifiable concentrates                                                     active ingredient:                                                                           1 to 20%, preferably 5 to 10%                                  surfactant:    5 to 30%, preferably 10 to 20%                                 liquid carrier:                                                                              50 to 94%, preferably 70 to 85%                                Dusts                                                                         active ingredient:                                                                           0.1 to 10%, preferably 0.1 to 1%                               solid carrier: 99.9 to 90%, preferably 99.9 to 99%                            Suspension concentrates                                                       active ingredient:                                                                           5 to 75%, preferably 10 to 50%                                 water:         94 to 24%, preferably 88 to 30%                                surfactant:    1 to 40%, preferably 2 to 30%                                  Wettable powders                                                              active ingredient:                                                                           0.5 to 90%, preferably 1 to 80%                                surfactant:    0.5 to 20%, preferably 1 to 15%                                solid carrier: 5 to 95%, preferably 15 to 90%                                 Granulates                                                                    active ingredient:                                                                           0.5 to 30%, preferably 3 to 15%                                solid carrier: 99.5 to 70%, preferably 97 to 85%                              ______________________________________                                    

The compositions may also contain further auxiliaries such asstabilisers, antifoams, preservatives, viscosity regulators, binders,tackifiers as well as fertilisers or other active ingredients forobtaining special effects.

The following Examples serve to illustrate the invention but do notlimit the invention.

PREPARATION EXAMPLES Example P11-(2,6-diisopropylphenyl)-4-isopropyl-5-thioxo-2-tetrazoline ##STR10##

A mixture of 5.6 g of1-(2,6-diisopropylphenyl)-4-isopropyl-5-oxo-2-tetrazoline and 5.1 g of2,4-bis-(4-methoxyphenyl)-1,3-dithia-2,4-diphosphetane-2,4-disulfide(Lawesson's reagent) are heated at reflux for 24 hours in 60 ml of drytoluene. After evaporating off the solvent, the residue is purified bychromatography on 500 g of silica gel with hexane/ethyl acetate (19:1)as eluant. Crystallisation from hexane yields 4.2 g of1-(2,6-diisopropylphenyl)-4-isopropyl-5-thioxo-2-tetrazoline in the formof colourless crystals, m.p. 109°-111° C.

Example P2 1-(2,6-diisopropylphenyl)-4-isopropyl-5-oxo-2-tetrazoline##STR11##

a) 1-(2,6-diisopropylphenyl)-5-oxo-2-tetrazoline. 37.1 g of2,6-diisopropylphenyl isocyanate and 50 ml of trimethylsilyl azide arestirred for 24 hours at +140° C. The mixture is then cooled to roomtemperature and stirred with 250 ml of toluene and with 250 ml of water.After 1 hour, the phases are separated and the aqueous phase isextracted with toluene. The combined organic phases are extracted fourtimes with 250 ml of 15% sodium hydroxide solution each time, and thenthe aqueous phases are combined and washed with ether. Afteracidification with semi-concentrated hydrochloric acid, crude1-(2,6-diisopropylphenyl)-5-oxo-2-tetrazoline precipitates. This isrecrystallised from a mixture of hexane and toluene in a ratio of 10:1.Melting point 177°-178.5°.

b) 14.3 g of 1-(2,6-diisopropylphenyl)-5-oxo-2-tetrazoline, 12.8 g ofisopropyl iodide and 10.4 g of pulverised potassium carbonate aredissolved in 140 ml of dimethylformamide and stirred for 2 hours at +60°C. The resulting suspension is poured onto water and extracted threetimes with ether. The combined ethereal phases are washed with water andsaturated sodium chloride solution, dried over Na₂ SO₄ and concentratedby evaporation. In order to remove the1-(2,6-diisopropylphenyl)-5-isopropoxy-tetrazole formed as by-product,the mixture is chromatographed on silica gel with the eluant CH₂ Cl₂/cyclohexane (3:1). In this manner 8.7 g of1-(2,6-diisopropylphenyl)-4-isopropyl-5-oxo-2-tetrazoline having amelting point of 60°-62° C. are obtained.

The intermediates of formulae II and VIII and compounds of formula Ilisted in the following Tables 1 and 2 are obtained in an analogousmanner.

                                      TABLE 1                                     __________________________________________________________________________     ##STR12##                                                                    Comp.                                                                         No. R.sup.1       R.sup.2                                                                             R.sup.3   R.sup.4                                                                             R.sup.5      physical                 __________________________________________________________________________                                                         data                     1.01                                                                              C.sub.3 H.sub.7 -i                                                                          C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     H            m.p. 109-111°                                                          C.                       1.02                                                                              C.sub.3 H.sub.7 -i                                                                          C.sub.3 H.sub.7 -i                                                                  6-C.sub.2 H.sub.5                                                                       H     H            n.sub.D.sup.23 =                                                              1.5483                   1.03                                                                              C.sub.3 H.sub.7 -i                                                                          C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     4-OC.sub.6 H.sub.5                                                                         m.p.                                                                          110.5-112°                                                             C.                       1.04                                                                              CH.sub.3      C.sub.3 H.sub.7 -i                                                                  6-C.sub.2 H.sub.5                                                                       H     H            m.p.                                                                          63.5-65.5°                                                             C.                       1.05                                                                              CH.sub.2C(CH.sub.3).sub.3                                                                   C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     4-OC.sub.6 H.sub.5                                                                         m.p. 136-138°                                                          C.                       1.06                                                                              C.sub.3 H.sub.7 -i                                                                          C.sub.5 H.sub.9 -cycl.                                                              6-C.sub.3 H.sub.7 -i                                                                    H     H            m.p. 77.5-78°                                                          C.                       1.07                                                                              C.sub.4 H.sub.9 -s                                                                          C.sub.5 H.sub.9 -cycl.                                                              6-C.sub.3 H.sub.7 -i                                                                    H     H            m.p.                                                                          69.5-71.5°                                                             C.                       1.08                                                                              C.sub.2 H.sub.5                                                                             C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     4-OC.sub.6 H.sub.5                                                                         m.p. 67.5-69°                                                          C.                       1.09                                                                              CH(CH.sub.3)COOCH.sub.3                                                                     C.sub.3 H.sub.7 -i                                                                  6-CH.sub.3 H.sub.7 -i                                                                   H     H            m.p. 51-54°                                                            C.                       1.10                                                                              C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                            6-C.sub.3 H.sub.7 -i                                                                    H     H            n.sub.D.sup.22 =                                                              1.5505                   1.11                                                                              C.sub.3 H.sub.7 -i                                                                          C.sub.2 H.sub.5                                                                     H         H     H            n.sub.D.sup.24,5 =                                                            1.5668                   1.12                                                                              CH.sub.2 C(CH.sub.3).sub.3                                                                  CH.sub.3                                                                            6-C.sub.3 H.sub.7 -i                                                                    H     H            m.p. 85.5-87°                                                          C.                       1.13                                                                              C.sub.5 H.sub.9 -cycl.                                                                      C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     4-OC.sub.6 H.sub.5                                                                         m.p. 97-98.5°                                                          C.                       1.14                                                                              C.sub.3 H.sub.7 -i                                                                          C.sub.2 H.sub.5                                                                     6-C.sub.2 H.sub.5                                                                       H     H            n.sub.D.sup.24 =                                                              1.5536                   1.15                                                                              CH.sub.2 C(CH.sub.3).sub.3                                                                  C.sub.3 H.sub.7 -i                                                                  6-C.sub.2 H.sub.5                                                                       H     H            n.sub.D.sup.23 =                                                              1.5418                   1.16                                                                              C.sub.4 H.sub.9 -s                                                                          C.sub.3 H.sub.7 -i                                                                  6-C.sub.2 H.sub.5                                                                       H     H                                     1.17                                                                              C.sub.5 H.sub.9 -cycl.                                                                      C.sub.3 H.sub.7 -i                                                                  6-C.sub.2 H.sub.5                                                                       H     H                                     1.18                                                                              CH.sub.2 C(CH.sub.3).sub.3                                                                  C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     H            m.p. 58-60°                                                            C.                       1.19                                                                              C.sub.4 H.sub.9 -s                                                                          C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     H                                     1.20                                                                              C.sub.4 H.sub.9 -t                                                                          C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     H                                     1.21                                                                              C.sub.5 H.sub.9 -cycl.                                                                      C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     H                                     1.22                                                                              CH.sub.2C.sub.3 H.sub.5 -cycl.                                                              C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     H                                     1.23                                                                              C(CH.sub.3).sub.2C.sub.2 H.sub. 5                                                           C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     H                                     1.24                                                                              CH(C.sub.2 H.sub.5).sub.2                                                                   C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     H                                     1.25                                                                              CH(CH.sub.3)C.sub.6 H.sub.13 -n                                                             C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     H                                     1.26                                                                              C.sub.6 H.sub.11 -cycl.                                                                     C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     H                                     1.27                                                                               ##STR13##    C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     H            m.p. 72-73°                                                            C.                       1.28                                                                              CH.sub.2 C(CH.sub.3).sub.3                                                                  C.sub.2 H.sub.5                                                                     H         H     H            n.sub.D.sup.20,5 =                                                            1.5560                   1.29                                                                              C.sub.4 H.sub.9 -s                                                                          CH.sub.3                                                                            6-C.sub.3 H.sub.7 -i                                                                    H     H            n.sub.D.sup.21,5 =                                                            1.5467                   1.30                                                                              CH.sub.2C.sub.3 H.sub.5 -cycl.                                                              C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     4-OC.sub.6 H.sub.5                                                                         m.p. 95.5-97°                                                          C.                       1.31                                                                              C.sub.4 H.sub.9 -s                                                                          C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     4-CH.sub.2 C.sub.6                                                                         m.p. 100-102°                                                          C.                       1.32                                                                              CH.sub.2 C(CH.sub.3).sub.3                                                                  C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     4-CH.sub.2 C.sub.6 H.sub.5                                                                 m.p.                                                                          145-146.5°                                                             C.                       1.33                                                                              C.sub.4 H.sub.9 -i                                                                          C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     4-CH.sub.2 C.sub.6 H.sub.5                                                                 m.p. 94-96°                                                            C.                       1.34                                                                              CH.sub.2C.sub.6 H.sub.5                                                                     C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     H                                     1.35                                                                              CH(CH.sub.3)C.sub.6 H.sub.5                                                                 C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     H                                     1.36                                                                              CH(CH.sub.3)CHCH.sub.2                                                                      C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     H                                     1.37                                                                              CH.sub.2CHCH.sub.2                                                                          C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     H                                     1.38                                                                              CH(CH.sub.3)CH.sub.2 OCH.sub.3                                                              C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     H            n.sub.D.sup.22.5 =                                                            1.5380                   1.39                                                                               ##STR14##    C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     H                                     1.40                                                                              C.sub.3 H.sub. 7 -i                                                                         C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    4-CH.sub.3                                                                          H                                     1.41                                                                              C.sub.3 H.sub.7 -i                                                                          C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    4-C.sub.3 H.sub.7 -i                                                                H                                     1.42                                                                              C.sub.4 H.sub.9 -s                                                                          C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    4-CH.sub.3                                                                          H                                     1.43                                                                              C.sub.3 H.sub.7 -i                                                                          C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    4-CCH H                                     1.44                                                                              C.sub.3 H.sub.7 -i                                                                          C.sub.3 H.sub.7 -i                                                                  6-CH(CH.sub.3)OCH.sub.3                                                                 H     H                                     1.45                                                                              C.sub.4 H.sub.9 -s                                                                          C.sub.3 H.sub.7 -i                                                                  6-CH(CH.sub.3)OCH.sub.3                                                                 H     H                                     1.46                                                                              C.sub.3 H.sub.7 -i                                                                          C.sub.2 H.sub.5                                                                     6-C.sub.4 H.sub.9 -s                                                                    H     H                                     1.47                                                                              C.sub.4 H.sub.9 -s                                                                          C.sub.2 H.sub.5                                                                     6-C.sub.4 H.sub.9 -s                                                                    H     H                                     1.48                                                                              CH.sub.2 C(CH.sub.3).sub.3                                                                  C.sub.2 H.sub.5                                                                     6-C.sub.4 H.sub.9 -s                                                                    H     H                                     1.49                                                                              C.sub.4 H.sub.9 -s                                                                          C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     4-OC.sub.6 H.sub.5                    1.50                                                                              C.sub.4 H.sub.9 -t                                                                          C.sub. 3 H.sub.7 -i                                                                 6-C.sub.3 H.sub.7 -i                                                                    H     4-OC.sub.6 H.sub.5                    1.51                                                                              C(CH.sub.3).sub.2C.sub.2 H.sub.5                                                            C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     4-OC.sub.6 H.sub.5                    1.52                                                                              C.sub.3 H.sub.7 -i                                                                          C.sub.5 H.sub.9 -cycl.                                                              6-C.sub.3 H.sub.7 -i                                                                    H     4-OC.sub.6 H.sub.5                                                                         n.sub.D.sup.23 =                                                              1.5656                   1.53                                                                              C.sub.4 H.sub.9 -s                                                                          C.sub.5 H.sub.9 -cycl.                                                              6-C.sub.3 H.sub.7 -i                                                                    H     4-OC.sub.6 H.sub.5                                                                         n.sub.D.sup.25 =                                                              1.5647                   1.54                                                                              CH.sub.2 C(CH.sub.3).sub.3                                                                  C.sub.5 H.sub.9 -cycl.                                                              6-C.sub.3 H.sub.7 -i                                                                    H     4-OC.sub.6 H.sub.5                    1.55                                                                              C.sub.6 H.sub.11 -cycl.                                                                     C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     4-OC.sub.6 H.sub.5                    1.56                                                                              CH(CH.sub.3)C.sub.6 H.sub.5                                                                 C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     4-OC.sub.6 H.sub.5                    1.57                                                                              C.sub.3 H.sub.7 -i                                                                          C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     4-OC.sub.6 H.sub.4 -2'-F                                                                   m.p.                                                                          116.5-117.5°                                                           C.                       1.58                                                                              C.sub.4 H.sub. 9 -s                                                                         C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     4-OC.sub.6 H.sub.4 -2'-F                                                                   m.p. 77-79°                                                            C.                       1.59                                                                              CH.sub.2 C(CH.sub.3).sub.3                                                                  C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     4-OC.sub.6 H.sub.4 -2'-F                                                                   m.p.                                                                          145.5-146.5°                                                           C.                       1.60                                                                              C.sub.4 H.sub.9 -t                                                                          C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     4-OC.sub.6 H.sub.4 -2'-F              1.61                                                                              CH(CH.sub.3)C.sub.6 H.sub.5                                                                 C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     4-OC.sub.6 H.sub.4 -2'-F              1.62                                                                              C.sub.5 H.sub.9 -cycl.                                                                      C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     4-OC.sub.6 H.sub.4 -2'-F              1.63                                                                              C.sub.3 H.sub.7 -i                                                                          C.sub.5 H.sub.9 -cycl.                                                              6-C.sub.3 H.sub.7 -i                                                                    H     4-OC.sub.6 H.sub.4 -2'-F                                                                   m.p. 92.5-94°                                                          C.                       1.64                                                                              C.sub.4 H.sub.9 -s                                                                          C.sub.5 H.sub.9 -cycl.                                                              6-C.sub.3 H.sub.7 -i                                                                    H     4-OC.sub.6 H.sub.4 -2'-F                                                                   Smp. 63-66°                                                            C.                       1.65                                                                              CH.sub.2 C(CH.sub.3).sub.3                                                                  C.sub.5 H.sub.9 -cycl.                                                              6-C.sub.3 H.sub.7 -i                                                                    H     4-OC.sub.6 H.sub.4 -2'-F                                                                   Smp. 101-103°                                                          C.                       1.66                                                                              C.sub.4 H.sub.9 -t                                                                          C.sub.5 H.sub.9 -cycl.                                                              6-C.sub.3 H.sub.7 -i                                                                    H     4-OC.sub.6 H.sub.4 -2'-F              1.67                                                                              C.sub.4 H.sub.11 -cycl.                                                                     C.sub.5 H.sub.9 -cycl.                                                              6-C.sub.3 H.sub.7 -i                                                                    H     4-OC.sub.6 H.sub.4 -2'-F              1.68                                                                              C.sub.3 H.sub.7 -i                                                                          C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     4-OC.sub.6 H.sub.4 -3'-F              1.69                                                                              C.sub.4 H.sub.9 -s                                                                          C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     4-OC.sub.6 H.sub.4 -3'-F              1.70                                                                              C.sub.5 H.sub.9 -cycl.                                                                      C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     4-OC.sub.6 H.sub.4 -3'-F              1.71                                                                              CH.sub.2 C(CH.sub.3).sub.3                                                                  C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     4-OC.sub.6 H.sub.4 -3'-F              1.72                                                                              C.sub.3 H.sub.7 -i                                                                          C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     4-OC.sub.6 H.sub.4 -4'-F              1.73                                                                              C.sub.4 H.sub.9 -s                                                                          C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     4-OC.sub.6 H.sub.4 -4'-F              1.74                                                                              CH.sub.2 C(CH.sub.3).sub.3                                                                  C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     4-OC.sub.6 H.sub.4 -4'-F              1.75                                                                              C.sub.5 H.sub.9 -cycl.                                                                      C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     4-OC.sub.6 H.sub.4 -4'-F              1.76                                                                              C.sub.3 H.sub.7 -i                                                                          C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    4-SCH.sub.3                                                                         H                                     1.77                                                                              CH.sub.2 C(CH.sub.3).sub.3                                                                  C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    4-SCH.sub.3                                                                         H                                     1.78                                                                              C.sub.4 H.sub.9 -s                                                                          C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    4-SCH.sub.3                                                                         H                                     1.79                                                                              C.sub.3 H.sub.7 -i                                                                          C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    4-Br  H                                     1.80                                                                              C.sub.3 H.sub.7 -i                                                                          C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    4-CN  H                                     1.81                                                                              C.sub.4 H.sub.9 -t                                                                          C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     4-CH.sub.2 C.sub.6 H.sub.5            1.82                                                                              C(CH.sub.3)C.sub.2 H.sub.5                                                                  C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     4-CH.sub.2 C.sub.6 H.sub. 5           1.83                                                                              CH(CH.sub.3)C.sub.6 H.sub.5                                                                 C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     4-CH.sub.2 C.sub.6 H.sub.5            1.84                                                                              C.sub.5 H.sub.9 -cycl.                                                                      C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     4-CH.sub.2 C.sub.6 H.sub.5            1.85                                                                              C.sub.6 H.sub.11 -cycl.                                                                     C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     4-CH.sub.2 C.sub.6 H.sub.5            1.86                                                                              C.sub.3 H.sub.7 -i                                                                          C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     4-CH(CH.sub.3)C.sub.6 H.sub.5         1.87                                                                              C.sub.4 H.sub.9 -s                                                                          C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     4-CH(CH.sub.3)C.sub.6 H.sub.5         1.88                                                                              CH.sub.2 C(CH.sub.3).sub.3                                                                  C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     4-CH(CH.sub.3)C.sub.6 H.sub.5         1.89                                                                              C.sub.3 H.sub.7 -i                                                                          C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     4-C.sub.6 H.sub.5                     1.90                                                                              C.sub.4 H.sub.9 -s                                                                          C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     4-C.sub.6 H.sub.5                     1.91                                                                              C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                            6-CH.sub.3                                                                              H                                                                                    ##STR15##                            1.92                                                                              C.sub.4 H.sub.9 -s                                                                          CH.sub.3                                                                            6-CH.sub.3                                                                              H                                                                                    ##STR16##                            1.93                                                                              C.sub.5 H.sub.9 -cycl.                                                                      CH.sub.3                                                                            6-CH.sub.3                                                                              H                                                                                    ##STR17##                            1.94                                                                              C.sub.3 H.sub.7 -i                                                                          C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     4-SC.sub.6 H.sub.5                    1.95                                                                              C.sub.4 H.sub.9 -s                                                                          C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     4-SC.sub.6 H.sub.5                    1.96                                                                              C.sub.3 H.sub.7 -i                                                                          C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     4-N(CHO)C.sub.6 H.sub.5               1.97                                                                              C.sub.4 H.sub.9 -s                                                                          C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     4-N(CHO)C.sub.6 H.sub.5               1.98                                                                              CH.sub.2 C(CH.sub.3 ).sub.3                                                                 C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     4-N(CHO)C.sub.6 H.sub.5               1.99                                                                              C.sub.5 H.sub.9 -cycl.                                                                      C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     4-N(CHO)C.sub.6 H.sub.5               1.100                                                                             C.sub.6 H.sub.11 -cycl.                                                                     C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     4-N(CHO)C.sub.6 H.sub.5               1.101                                                                             C.sub.4 H.sub.9 -t                                                                          C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     4-N(CHO)C.sub.6 H.sub.5               1.102                                                                             C.sub.3 H.sub.7 -i                                                                          C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     4-N(CHO)C.sub.6 H.sub.4 -2'-F         1.103                                                                             C.sub.4 H.sub.9 -s                                                                          C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     4-N(CHO)C.sub.6 H.sub.4 -2'-F         1.104                                                                             CH.sub.2 C(CH.sub.3).sub.3                                                                  C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     4-N(CHO)C.sub.6 H.sub.4 -2'-F         1.105                                                                             C.sub.3 H.sub.7 -i                                                                          C.sub.4 H.sub.9 -t                                                                  6-CH.sub.3                                                                              H     H            m.p. 89.5-91°                                                          C.                       1.106                                                                             C.sub.4 H.sub.9 -s                                                                          C.sub.4 H.sub.9 -t                                                                  6-CH.sub.3                                                                              H     H            m.p. 76-77°                                                            C.                       1.107                                                                             CH.sub.2 C(CH.sub.3).sub.3                                                                  C.sub.4 H.sub.9 -t                                                                  6-CH.sub.3                                                                              H     H            m.p. 116-119°                                                          C.                       1.108                                                                             C(CH.sub.3).sub.2CCH                                                                        C.sub.3 H.sub.7 -i                                                                  6-C.sub.2 H.sub.5                                                                       H     H                                     1.109                                                                             C(CH.sub.3).sub.2CCH                                                                        C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     H                                     1.110                                                                             C(CH.sub.3).sub.2CCH                                                                        C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     4-OC.sub.6 H.sub.5                    1.111                                                                             C(CH.sub.3).sub.2CCH                                                                        C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     4-OC.sub.6 H.sub.4 -2'-F              1.112                                                                             C(CH.sub.3).sub.2CHCH                                                                       C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     H                                     1.113                                                                             C(CH.sub.3).sub.2CHCH                                                                       C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     4-OC.sub.6 H.sub.5                    1.114                                                                             C(CH.sub.3).sub.3CCH                                                                        C.sub.2 H.sub. 5                                                                    6-C.sub.4 H.sub.9 -s                                                                    H     H                                     1.115                                                                             C(CH.sub.3).sub.3CCH                                                                        C.sub.2 H.sub.5                                                                     6-C.sub.4 H.sub.9 -s                                                                    H     4-OC.sub.6 H.sub.5                    1.116                                                                             CH.sub.3      C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     4-OC.sub.6 H.sub.5                                                                         m.p. 80-83.5°                                                          C.                       1.117                                                                             C.sub.4 H.sub.9 -s                                                                          C.sub.2 H.sub.5                                                                     6-C.sub.2 H.sub.5                                                                       H     H            m.p. 50-52°                                                            C.                       1.118                                                                             C.sub.3 H.sub.7 -i                                                                          CH.sub.3                                                                            6-CH.sub.3                                                                              H     H            m.p. 101-103°                                                          C.                       1.119                                                                             C.sub.4 H.sub.2 -s                                                                          CH.sub.3                                                                            6-CH.sub.3                                                                              H     H            m.p. 44-46°                                                            C.                       1.120                                                                             C.sub.4 H.sub.9 -s                                                                          C.sub.2 H.sub.5                                                                     H         H     H            n.sub.D.sup.23 =                                                              1.5607                   1.121                                                                             C.sub.4 H.sub.9 -t                                                                          C.sub.5 H.sub.9 -cycl.                                                              6-C.sub.3 H.sub.7 -i                                                                    H     4-OC.sub.6 H.sub.5                                                                         m.p. 101-103°                                                          C.                       1.122                                                                             C.sub.3 H.sub.7 -i                                                                          C.sub.4 H.sub.9 -s                                                                  6-C.sub.4 H.sub.9 -s                                                                    H     4-C.sub.6 H.sub.5                                                                          m.p. 119-121°                                                          C.                       1.123                                                                             CH(CH.sub.3)CH.sub.2OCH.sub.3                                                               C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     4-OC.sub.6 H.sub.5                                                                         m.p.                                                                          93.5-94.5°                                                             C.                       1.124                                                                             C.sub.3 H.sub.7 -i                                                                          C.sub.3 H.sub.7 -i                                                                  H         H     H                                     1.125                                                                             C.sub.4 H.sub.9 -s                                                                          C.sub.3 H.sub.7 -i                                                                  H         H     H                                     1.126                                                                             C.sub.4 H.sub.9 -s                                                                          C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     4-OC.sub.6 H.sub.4 -2'-Cl             1.127                                                                             C.sub.3 H.sub.7 -i                                                                          C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                                    H     4-OC.sub.6 H.sub.4 -2'-Cl             __________________________________________________________________________

                                      TABLE 2                                     __________________________________________________________________________     ##STR18##                                                                    Comp.                                                                         No. R.sup.1   R.sup.2                                                                             R.sup.3                                                                            R.sup.4                                                                         R.sup.5       physical data                        __________________________________________________________________________    2.01                                                                              C.sub.3 H.sub.7 -i                                                                      C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                               H H             m.p. 60-62° C.                2.02                                                                              C.sub.3 H.sub.7 -i                                                                      C.sub.3 H.sub.7 -i                                                                  6-C.sub.2 H.sub.5                                                                  H H             n.sub.D.sup.23 = 1,5141              2.03                                                                              C.sub.3 H.sub.7 -i                                                                      C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                               H 4-OC.sub.6 H.sub.5                                                                          n.sub.D.sup.21.5 = 1.5429            2.04                                                                              CH.sub.3  C.sub.3 H.sub.7 -i                                                                  6-C.sub.2 H.sub.5                                                                  H H             m.p. 52.5-55                         2.05                                                                              CH.sub.2 C(CH.sub.3).sub.3                                                              C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                               H 4-OC.sub.6 H.sub.5                                                                          *)                                   2.06                                                                              C.sub.3 H.sub.7 -i                                                                      C.sub.5 H.sub.9 -cycl.                                                              6-C.sub.3 H.sub.7 -i                                                               H H             n.sub.D.sup.24 = 1.5262              2.07                                                                              C.sub.3 H.sub.7 -s                                                                      C.sub.5 H.sub.9 -cycl.                                                              6-C.sub.3 H.sub.7 -i                                                               H H             n.sub.D.sup.24 = 1.5236              2.08                                                                              C.sub.2 H.sub.5                                                                         C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                               H 4-OC.sub.6 H.sub.5                                                                          m.p. 80-81° C.                2.09                                                                              CH(CH.sub.3)COOCH.sub.3                                                                 C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                               H H             m.p. 58-60° C.                2.10                                                                              C.sub.3 H.sub.7 -i                                                                      CH.sub.3                                                                            6-C.sub.3 H.sub.7 -i                                                               H H             n.sub.D.sup.24 = 1.5147              2.11                                                                              C.sub.3 H.sub.7 -i                                                                      C.sub.2 H.sub.5                                                                     H    H H             n.sub.D.sup.22 = 1.5260              2.12                                                                              CH.sub.2 C(CH.sub.3).sub.3                                                              CH.sub.3                                                                            6-C.sub.3 H.sub.7 -i                                                               H H             *)                                   2.13                                                                              C.sub.5 H.sub.9 -cycl.                                                                  C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                               H 4-OC.sub. 6 H.sub.5                                                                         n.sub.D.sup.23.5 = 1.5493            2.14                                                                              CH.sub.2 C(CH.sub.3).sub.3                                                              C.sub.3 H.sub.7 -i                                                                  6-C.sub.2 H.sub.5                                                                  H H             *)                                   2.15                                                                              CH.sub.2 C(CH.sub.3).sub.3                                                              C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                               H H             *)                                   2.16                                                                              CH.sub.2 C(CH.sub.3).sub.3                                                              C.sub.2 H.sub.5                                                                     H    H H             *)                                   2.17                                                                              C.sub.4 H.sub.9 -s                                                                      CH.sub.3                                                                            6-C.sub.3 H.sub.7 -i                                                               H H             *)                                   2.18                                                                              CH.sub.2C.sub.3 H.sub.5 cycl.                                                           C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                               H 4-OC.sub.6 H.sub.5                                                                          m.p. 118.5-120° C.            2.19                                                                              C.sub.4 H.sub.9 -s                                                                      C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                               H 4-CH.sub.2 C.sub.6 H.sub.5                                                                  m.p. 71-73° C.                2.20                                                                              CH.sub.2 C(CH.sub.3).sub.3                                                              C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                               H 4-CH.sub.2 C.sub.6 H.sub.5                                                                  *)                                   2.21                                                                              C.sub.3 H.sub.7 -i                                                                      C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                               H 4-CH.sub.2 C.sub.6 H.sub.5                                                                  *)                                   2.22                                                                              CH.sub.3  C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                               H 4-OC.sub.6 H.sub.5                                                                          m.p. 107-108° C.              2.23                                                                              H         C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                               H H             m.p. 177-178.5° C.            2.24                                                                              H         C.sub.3 H.sub.7 -i                                                                  6-C.sub.2 H.sub.5                                                                  H H             m.p. 124-125° C.              2.25                                                                              H         C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                               H 4-OC.sub.6 H.sub.5                                                                          m.p. 221-224° C.              2.26                                                                              H         C.sub.5 H.sub.9 -cycl.                                                              6-C.sub.3 H.sub.7 -i                                                               H H             m.p. 166-167.5° C.            2.27                                                                              H         CH.sub.3                                                                            6-C.sub.3 H.sub.7 -i                                                               H H             m.p. 147.5-148.5° C.          2.28                                                                              H         C.sub.2 H.sub.5                                                                     H    H H             m.p. 117-118.5° C.            2.29                                                                              H         C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                               H 4-CH.sub.2 C.sub.6 H.sub.5                                                                  m.p. 199-201° C.              2.30                                                                              H         C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                               H                                                                                ##STR19##    m.p. 218-220° C.              2.31                                                                              CH.sub.2 C(CH.sub.3).sub.3                                                              C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                               H                                                                                ##STR20##    *)                                   2.32                                                                              C.sub.3 H.sub.7 -i                                                                      C.sub.2 H.sub.5                                                                     6-C.sub.2 H.sub.5                                                                  H H             *)                                   2.33                                                                              H         C.sub.2 H.sub.5                                                                     6-C.sub.2 H.sub.5                                                                  H H             m.p. 92-94° C.                2.34                                                                              C.sub.4 H.sub.9 -s                                                                      C.sub.2 H.sub.5                                                                     6-C.sub.2 H.sub.5                                                                  H H             *)                                   2.35                                                                              C.sub.3 H.sub.7 -i                                                                      CH.sub.3                                                                            6-CH.sub.3                                                                         H H             *)                                   2.36                                                                              H         CH.sub.3                                                                            6-CH.sub.3                                                                         H H             m.p. 142-144° C.              2.37                                                                              C.sub.4 H.sub.9 -s                                                                      CH.sub.3                                                                            6-CH.sub.3                                                                         H H             *)                                   2.38                                                                              CH.sub.2 C(CH.sub.3).sub.3                                                              CH.sub.3                                                                            6-C.sub.4 H.sub.9 -t                                                               H H             *)                                   2.39                                                                              H         CH.sub.3                                                                            6-C.sub.4 H.sub.9 -t                                                               H H             m.p. 198-199.5° C.            2.40                                                                              C.sub.4 H.sub.9 -s                                                                      C.sub.2 H.sub.5                                                                     H    H H             *)                                   2.41                                                                              CH.sub.2 C(CH.sub.3).sub.3                                                              C.sub.5 H.sub.9 -cycl.                                                              6-C.sub.3 H.sub.7 -i                                                               H 4-OC.sub.6 H.sub.5                                                                          *)                                   2.42                                                                              H         C.sub.5 H.sub.9 -cycl.                                                              6-C.sub.3 H.sub.7 -i                                                               H 4-OC.sub.6 H.sub. 5                                                                         m.p. 214.5-216° C.            2.43                                                                              C.sub.3 H.sub.7 -i                                                                      C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                               H                                                                                ##STR21##    m.p. 101-102° C.              2.44                                                                              C.sub.4 H.sub.9 -s                                                                      C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                               H                                                                                ##STR22##    m.p. 66-68° C.                2.45                                                                              C.sub.3 H.sub.7 -i                                                                      CH.sub.3                                                                            6-C.sub.3 H.sub.9 -t                                                               H H             n.sub.D.sup.25 = 1.5179              2.46                                                                              C.sub.3 H.sub.7 -i                                                                      C.sub.4 H.sub.9 -s                                                                  6-C.sub.4 H.sub.9 -s                                                               H 4-C.sub.6 H.sub.5                                                                           *)                                   2.47                                                                              H         C.sub.4 H.sub.9 -s                                                                  6-C.sub.4 H.sub.9 -s                                                               H 4-C.sub.6 H.sub.5                                                                           m.p. 170-172° C.              2.48                                                                              C.sub.4 H.sub.9 -s                                                                      CH.sub.3                                                                            6-C.sub.4 H.sub.9 -t                                                               H H             n.sub.D.sup.20 = 1.5180              2.49                                                                              C.sub.3 H.sub.7 -i                                                                      C.sub.5 H.sub.9 -cycl.                                                              6-C.sub.3 H.sub.7 -i                                                               H 4-OC.sub.6 H.sub.5                                                                          n.sub.D.sup.22 = 1.5450              2.50                                                                              C.sub.4 H.sub.9 -s                                                                      C.sub.5 H.sub.9 -cycl.                                                              6-C.sub.3 H.sub.7 -i                                                               H 4-OC.sub.6 H.sub.5                                                                          n.sub.D.sup.21 = 1.5465              2.51                                                                              CH(CH.sub.3)CH.sub.2 OCH.sub.3                                                          C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                               H H             *)                                   2.52                                                                              CH(CH.sub.3)CH.sub.2 OCH.sub.3                                                          C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                               H 4-OC.sub.6 H.sub.5                                                                          *)                                   2.53                                                                              CH.sub.2 C(CH.sub.3).sub.3                                                              C.sub.5 H.sub.9 -cycl.                                                              6-C.sub.3 H.sub.7 -i                                                               H                                                                                ##STR23##    *)                                   2.54                                                                              H         C.sub.5 H.sub.9 -cycl.                                                              6-C.sub.3 H.sub.7 -i                                                               H                                                                                ##STR24##    m.p. 212-213.5° C.            2.55                                                                              C.sub.4 H.sub.9 -s                                                                      C.sub.5 H.sub.9 -cycl.                                                              6-C.sub.3 H.sub.7 -i                                                               H                                                                                ##STR25##    n.sub.D.sup.20 = 1.5398              2.56                                                                              C.sub.3 H.sub.7 -i                                                                      C.sub.5 H.sub.9 -cycl.                                                              6-C.sub.3 H.sub.7 -i                                                               H                                                                                ##STR26##    n.sub.D.sup.20 = 1.5435              2.57                                                                              C.sub.3 H.sub.7 -i                                                                      C.sub.3 H.sub.7 -i                                                                  H    H H                                                  2.58                                                                              C.sub.4 H.sub.9 -s                                                                      C.sub.3 H.sub.7 -i                                                                  H    H H                                                  2.59                                                                              H         C.sub.3 H.sub.7 -i                                                                  H    H H                                                  2.60                                                                              C.sub.3 H.sub.7 -i                                                                      C.sub.2 H.sub.5                                                                     6-C.sub.4 H.sub.9 -s                                                               H H                                                  2.61                                                                              C.sub.4 H.sub.9 -s                                                                      C.sub.2 H.sub.5                                                                     6-C.sub.4 H.sub.9 -s                                                               H H                                                  2.62                                                                              CH.sub.2 C(CH.sub.3).sub.3                                                              C.sub.2 H.sub.5                                                                     6-C.sub.4 H.sub.9 -s                                                               H H                                                  2.63                                                                              H         C.sub.2 H.sub.5                                                                     6-C.sub.4 H.sub.9 -s                                                               H H                                                  2.64                                                                              C.sub.3 H.sub.7 -i                                                                      C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                               H                                                                                ##STR27##                                         2.65                                                                              C.sub.4 H.sub.9 -s                                                                      C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                               H                                                                                ##STR28##                                         2.66                                                                              H         C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                               H                                                                                ##STR29##                                         2.67                                                                              C.sub.3 H.sub.7 -i                                                                      C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                               H 4-CH(CH.sub.3)C.sub.6 H.sub.5                                                               m.p. 67.5-69.5° C.            2.68                                                                              C.sub.4 H.sub.9 -s                                                                      C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                               H 4-CH(CH.sub.3)C.sub.6 H.sub.5                                                               n.sub.D.sup.21 = 1.5365              2.69                                                                              H         C.sub.3 H.sub.7 -i                                                                  6-C.sub.3 H.sub.7 -i                                                               H 4-CH(CH.sub.3)C.sub.6 H.sub.5                                                               m.p. 191.5-193.5° C.          2.70                                                                              C.sub.3 H.sub.7 -i                                                                      CH.sub.3                                                                            6-CH.sub.3                                                                         H                                                                                ##STR30##    *)                                   2.71                                                                              C.sub.4 H.sub.9 -s                                                                      CH.sub.3                                                                            6-CH.sub.3                                                                         H                                                                                ##STR31##    *)                                   2.72                                                                              H         CH.sub.3                                                                            6-CH.sub.3                                                                         H                                                                                ##STR32##    m.p. 175.5-179° C.            __________________________________________________________________________     *)yellow oils that can be used in the thionation reaction without being       further purified. These oils contain, in addition to the product              indicated, the isomeric 1phenyl-5-alkoxy-tetrazole of formula                 ##STR33##                                                                

FORMULATION EXAMPLES (throughout, percentages are by weight)

    ______________________________________                                        Example F1: Emulsifiable concentrates                                                                (a)    (b)                                             ______________________________________                                        compound No. 1.03      10%    25%                                             calcium dodecylbenzenesulfonate                                                                      --      5%                                             caster oil polyethylene glycol                                                                       25%     5%                                             ether (36 moles of ethylene oxide)                                            cyclohexanone          --     40%                                             butanol                15%    --                                              xylene mixture         --     25%                                             ethyl acetate          50%    --                                              ______________________________________                                    

Emulsions of any desired concentration can be produced from suchconcentrates by dilution with water.

    ______________________________________                                        Example F2: Solutions  (a)    (b)                                             ______________________________________                                        compound No. 1.01 10% 5%                                                      polyethylene glycol (mol. wt. 400)                                                                   70%    --                                              N-methyl-2-pyrrolidone 20%    20%                                             epoxidised coconut oil --      1%                                             petroleum fraction (boiling                                                                          --     74%                                             range 160-190° C.)                                                     ______________________________________                                    

These solutions are suitable for application in the form of micro-drops.

    ______________________________________                                        Example F3: Granulates                                                                             (a)    (b)                                               ______________________________________                                        compound No. 1.02     5%    10%                                               kaolin               94%                                                      highly dispersed silicic acid                                                                       1%                                                      attapulgite          --     90%                                               ______________________________________                                    

The active ingredient is dissolved in methylene chloride, the solutionis sprayed onto the carrier, and the solvent is subsequently evaporatedoff in vacuo.

    ______________________________________                                        Example F4: Extruder granulate                                                ______________________________________                                        compound No. 1.05  10%                                                        sodium lignosulfonate                                                                             2%                                                        carboxymethylcellulose                                                                            1%                                                        kaolin             87%                                                        ______________________________________                                    

The active ingredient is mixed and ground with the adjuvants, and themixture is subsequently moistened with water. The mixture is extrudedand then dried in a stream of air.

    ______________________________________                                        Example F5: Coated granulate                                                  ______________________________________                                        compound No. 1.04       3%                                                    polyethylene glycol (mol. wt. 400)                                                                    3%                                                    kaolin                 94%                                                    ______________________________________                                    

The finely ground active ingredient is uniformly applied, in a mixer, tothe kaolin moistened with polyethylene glycol. Non-dusty coatedgranulates are obtained in this manner.

    ______________________________________                                        Example F6: Dusts                                                                              (a)      (b)    (c)    (d)                                   ______________________________________                                        compound No. 1.03                                                                               2%       5%     5%     8%                                   highly dispersed silicic acid                                                                   1%       5%    --     --                                    talcum           97%      --     95%    --                                    kaolin           --       90%    --     92%                                   ______________________________________                                    

Ready-for-use dusts are obtained by homogeneously mixing the carrierswith the active ingredient and where appropriate grinding in a suitablemill.

    ______________________________________                                        Example F7: Wettable powders                                                                        (a)    (b)      (c)                                     ______________________________________                                        compound No. 1.06     20%    50%      75%                                     sodium lignosulfonate  5%     5%      --                                      sodium laurylsulfate   3%    --        5%                                     sodium diisobutylnaphthalene-                                                                       --      6%      10%                                     sulfonate                                                                     octylphenol polyethylene glycol                                                                     --      2%      --                                      ether (7-8 moles of ethylene oxide)                                           highly dispersed silicic acid                                                                        5%    10%      10%                                     kaolin                67%    27%      --                                      ______________________________________                                    

The active ingredient is throroughly mixed with the adjuvants and themixture is ground in a suitable mill, affording wettable powders whichcan be diluted with water to give suspensions of the desiredconcentration.

    ______________________________________                                        Example F8: Suspension concentrate                                            ______________________________________                                        compound No. 1.13          40%                                                ethylene glycol            10%                                                nonylphenol polyethylene glycol                                                                          6%                                                 ether (15 moles of ethylene oxide)                                            sodium lignosulfonate      10%                                                carboxymethylcellulose     1%                                                 37% aqueous formaldehyde solution                                                                        0.2%                                               silicone oil in the form of a 75%                                                                        0.8%                                               aqueous emulsion                                                              water                      32%                                                ______________________________________                                    

The finely ground active ingredient is homogeneously mixed with theadjuvants, giving a suspension concentrate from which suspensions of anydesired concentration can be obtained by dilution with water.

BIOLOGICAL EXAMPLES Example B1 Action against Diabrotica balteata larvae

Maize seedlings are sprayed with an aqueous emulsion spray formulationcontaining 400 ppm of the active ingredient. When the spray coating hasdried, the maize seedlings are each populated with 10 larvae ofDiabrotica balteata in the L₂ stage and placed in a plastics container.Evaluation is carried out six days later. The percentage reduction inpopulation (% effect) is ascertained by comparing the number of deadlarvae on the treated plants with the number of dead larvae on theuntreated plants.

Compounds from Table 1 exhibit a good activity against Diabroticabalteata in this test. Compounds 1.01, 1.02, 1.03, 1.05, 1.10, 1.12,1.33, 1.30, 1.18, 1.31, 1.59, 1.14, 1.107, 1.57, 1.58, 1.105, 1.106 and1.52 are more than 80% effective.

Example B2 Action against Tetranychus urticae

Young bean plants are populated with a mixed population of Tetranychusurticae and sprayed 1 day later with an aqueous emulsion sprayformulation containing 400 ppm of the active ingredient. The plants arethen incubated for 6 days at 25° C. and subsequently evaluated. Thepercentage reduction in population (% effect) is ascertained bycomparing the number of dead eggs, larvae and adults on the treatedplants with that on the untreated plants.

Compounds from Table 1 exhibit a good activity against Tetranychusurticae in this test. Compounds 1.03, 1.05, 1.07, 1.13, 1.33, 1.30,1.31, 1.29, 1.57, 1.105 and 1.52 reduce the population by more than 80%.

Example B3 Action against Spodoptera littoralis caterpillars

Young soybean plants are sprayed with an aqueous emulsion sprayformulation containing 400 ppm of the active ingredient. When the spraycoating has dried the soybean plants are each populated with 10caterpillars of Spodoptera littoralis in the L₃ stage and placed in aplastics containers. The evaluation is carried out 3 days later. Thepercentage reduction in population and the percentage reduction infeeding damage (% effect) are ascertained by comparing the number ofdead caterpillars and the feeding damage, respectively, on the treatedand untreated plants.

Compounds from Table 1 exhibit a good activity against Spodopteralittoralis in this test. Compound 1.03 causes a reduction in populationof more than 80% even at 50 ppm.

Example B4 Action against Crocidolomia binotalis caterpillars

Young cabbage plants are sprayed with an aqueous emulsion sprayformulation containing 400 ppm of the active ingredient. When the spraycoating has dried the cabbage plants are each populated with 10caterpillars of Crocidolomia binotalis in the L₃ stage and placed in aplastics container. The evaluation is carried out 3 days later. Thepercentage reduction in population and the percentage reduction infeeding damage (% effect) are ascertained by comparing the number ofdead caterpillars and the feeding damage, respectively, on the treatedand untreated plants.

Compounds from Table 1 exhibit a good activity against Crocidolomiabinotalis in this test. Compound 1.03 is more than 80% effective even at50 ppm.

Example B5 Action against Anthonomus grandis adults

Young cotton plants are sprayed with an aqueous emulsion sprayformulation containing 400 ppm of the active ingredient. When the spraycoating has dried the cotton plants are each populated with 10Anthonomus grandis adults and placed in a plastics container. Theevaluation is carried out 3 days later. The percentage reduction inpopulation and the percentage reduction in feeding damage (% effect) areascertained by comparing the number of dead beetles and the feedingdamage, respectively, on the treated and untreated plants.

Compounds from Table 1 exhibit a good activity against Anthonomusgrandis in this test. Compound 1.03 is still more than 80% effectiveeven at 200 ppm.

Example B6 Systemic action against Nilaparvata lugens

Approximately 10-day-old rice plants are each placed in a plasticsbeaker which contains 20 ml of an aqueous emulsion formulation of thetest compound in a concentration of 50 ppm and which is closed with aperforated plastics lid. The root of each rice plant is pushed through ahole in the plastics lid into the aqueous test formulation. The riceplant is then populated with 20 nymphs of Nilaparvata lugens in the N₂to N₃ stage and covered with a plastics cylinder. The test is carriedout at 26° C. and approximately 60% relative humidity with a period ofexposure to light of 16 hours. After two and five days the number ofdead test insects is ascertained in comparison with untreated controls.

Compounds from Table 1 exhibit a good activity against Nilaparvatalugens in the above test. Compounds 1.01, 1.02, 1.03, 1.04, 1.06, 1.07,1.10, 1.12, 1.18, 1.29, 1.14, 1.107, 1.105 and 1.106 are 80-100%effective.

Example B7 Action against Nilaparvata lugens

Rice plants are treated with an aqueous emulsion spray formulationcontaining 400 ppm of the active ingredient. When the spray coating hasdried, the rice plants are each populated with cicada larvae in the L₂and L₃ stage. The evaluation is carried out 21 days later. Thepercentage reduction in population (% effect) is ascertained bycomparing the number of surviving cicadas on the treated plants with thenumber on the untreated plants.

Compounds from Table 1 exhibit a good activity against Nilaparvatalugens in this test. In particular, compounds 1.01, 1.02, 1.03, 1.06,1.05, 1.08, 1.07, 1.13, 1.12, 1.33, 1.30, 1.18, 1.32, 1.29, 1.27, 1.14,1.107, 1.57, 1.58, 1.105 and 1.106 are more than 80% effective.

Example B8 Action against Nephotettix cincticeps

Rice plants are treated with an aqueous emulsion spray formulationcontaining 400 ppm of the active ingredient. When the spray coating hasdried, the rice plants are each populated with cicada larvae in the L₂and L₃ stage. The evaluation is carried out 21 days later. Thepercentage reduction in population (% effect) is ascertained bycomparing the number of surviving cicadas on the treated plants with thenumber on untreated plants.

Compounds from Table 1 exhibit a good activity against Nephotettixcincticeps in this test. In particular, compounds 1.01, 1.03, 1.05,1.08, 1.33, 1.107, 1.57, 1.58, 1.105 and 1.106 are 80-100% effective.

Example B9 Action against Aphis craccivora

Pea seedlings are infested with Aphis craccivora and then sprayed with aspray formulation containing 400 ppm of the test compound and incubatedat 20° C. The evaluation is carried out 3 and 6 days later. Thepercentage reduction in population (% effect) is ascertained bycomparing the number of dead aphids on the treated plants with thenumber on the untreated plants.

Compounds from Table 1 exhibit a good activity against Aphis craccivorain this test. In particular, compounds 1.01, 1.02, 1.07, 1.11 and 1.14are more than 80% effective.

Example B10 Action against Boophilus microplus

Fully replete adult female ticks are affixed to a PVC plate and coveredwith a cottonwool swab. For the treatment, 10 ml of an aqueous testsolution containing 125 ppm of the test compound are poured over thetest organisms. The cottonwool swab is then removed and the ticks areincubated for 4 weeks for oviposition. The activity against Boophilusmicroplus is demonstrated by death or sterility of the females or, inthe case of eggs, by ovicidal action.

The compounds according to Table 1 exhibit a good activity againstBoophilus microplus in this test. In particular, compounds 1.01, 1.02,1.03, 1.05, 1.08, 1.13, 1.18, 1.30, 1.38, 1.33 and 1.59 are more than80% effective.

EXAMPLE B11: Action against Musca domestica

A sugar cube is so treated with a solution of the test substance thatthe concentration of test substance in the sugar after drying overnightis 250 ppm. This treated cube is placed with a wet cottonwool swab and10 adult (approximately 1-week-old) flies [species M. domestica;Schmidlin strain (organophosphate-resistant)] on an aluminium dish. Thewhole is covered with a beaker glass and left for 24 hours at 25° C. and50% humidity. The mortality rate is determined at the end of thisperiod.

The compounds of Table 1 exhibit a good activity against Musca domesticain this test. In particular, compounds 1.08, 1.30 and 1.58 are more than80% effective.

EXAMPLE B12: Action against Heliothis virescens caterpillars

Young soybean plants are sprayed with an aqueous emulsion sprayformulation containing 400 ppm of the active ingredient. When the spraycoating has dried, the soybean plants are each populated with 10caterpillars of Heliothis virescens in the first stage and placed in aplastics container. The evaluation is carried out 6 days later. Thepercentage reduction in population and the percentage reduction infeeding damage (% effect) is ascertained by comparing the number of deadcaterpillars and the feeding damage, respectively, on the treated anduntreated plants.

Compounds from Table 1 exhibit a good activity against Heliothisvirescens in this test. In particular, compounds 1.33 and 1.31 are morethan 80% effective.

What is claimed is:
 1. A-1-Phenyl-5-oxo-2-tetrazolines of formula II##STR34## in which R¹ is C₁ -C₈ alkyl, C₃ -C₆ alkenyl, C₃ -C₆ alkynyl,C₃ -C₆ cycloalkyl, C₅ -C₆ cycloalkenyl, C₁ -C₄ alkyl- orhalo-substituted C₃ -C₆ cycloalkyl, C₁ -C₄ alkyl-or halo-substituted C₅-C₆ cycloalkenyl, halo-, C₁ -C₄ alkoxy- or phenyl-substituted C₃ -C₆alkenyl, halo-, C₁ -C₄ alkoxy- or phenyl-substituted C₃ -C₈ alkynyl, orC₁ -C₈ alkyl that is substituted by halogen, C₁ -C₄ alkoxy, C₁ -C₄alkylthio, C₁ -C₄ alkoxycarbonyl, C₃ -C₆ cycloalkyl, phenyl, cyano,hydroxy, halophenyl or C₁ -C₄ alkylphenyl,R² is C₁ -C₆ alkyl, C₂ -C₆alkenyl, C₂ -C₆ alkynyl, C₃ -C₆ cycloalkyl, cyclopentenyl orcyclohexenyl, or is C₁ -C₆ alkyl that is substituted by halogen, by C₁-C₄ alkoxy or by C₁ -C₄ alkylthio, each of R³ and R⁴, independently ofthe other, is hydrogen, halogen, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄alkoxy, C₁ -C₄ alkylthio, C₃ -C₆ cycloalkyl, C₂ -C₄ alkenyl, C₂ -C₄alkynyl, C₂ -C₆ alkoxyalkyl, C₂ -C₆ alkylthioalkyl, C₁ -C₄ cyanoalkyl,phenyl-C₂ -C₄ alkenyl or phenyl-C₂ -C₄ alkynyl, or R³ and R⁴ togetherare a --CH═CH--CH═CH--, --CH₂ --CH═CH--, --(CH₂)₄ --, --(CH₂)₃ --,--O--CH₂ --O--, --O--CH₂ --CH₂ --O--, --CH₂ --O--CH₂ --, --(CH₂)₂--CH═CH--or --CH₂ --CH═CH--CH₂ -- bridge, each of which may besubstituted by one or two C₁ -C₄ alkyl groups, and R⁵ is hydrogen or a--Z--R⁶ group in which R⁶ is phenyl, naphthyl or pyridyl, or is phenyl,naphthyl or pyridyl each of which is substituted by one or twosubstituents from the group halogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₁ -C₄haloalkoxy, C₁ -C₄ haloalkyl, C₁ -C₄ -alkylthio, C₁ -C₄ haloalkylthio,di-C₁ -C₄ alkylamino, nitro, cyano, C₁ -C₄ alkoxycarbonyl and C₁ -C₄alkylcarbonyl, and Z is oxygen, sulfur, a direct bond, --NH--, --N(C₁-C₂ alkyl)--, --N(CHO)--, --CH₂ --, --CH(CH₃)-- or --C(CH₃)₂ --. 2.A-1-Phenyl-5-oxo-2-tetrazolines of formula VIII ##STR35## in which R² isC₁ -C₆ alkyl, C₂ -C₆ alkenyl, C₂ -C₆ alkynyl, C₃ -C₆ cycloalkyl,cyclopententyl or cyclohexenyl, or is C₁ -C₆ alkyl that is substitutedby halogen, by C₁ -C₄ alkoxy or by C₁ -C₄ alkylthio,each of R³ and R⁴,independently of the other, is hydrogen, halogen, C₁ -C₄ alkyl, C₁ -C₄haloalkyl, C₁ -C₄ alkoxy, C₁ -C₄ alkylthio, C₃ -C₆ cycloalkyl, C₂ -C₄alkenyl, C₂ -C₄ alkynyl, C₂ -C₆ alkoxyalkyl, C₂ -C₆ alkylthioalkyl, C₁-C₄ cyanoalkyl, phenyl-C₂ -C₄ alkenyl or phenyl-C₂ -C₄ alkynyl, or R³and R⁴ together are a --CH═CH--CH═CH--, --CH₂ --CH═CH--, --(CH₂)₄ --,--(CH₂)₃ --, --O--CH₂ --O--, --O--CH₂ --CH₂ --O--, --CH₂ --O--CH₂ --,--(CH₂)₂ --CH═CH-- or --CH₂ --CH═CH--CH₂ -- bridge, each of which may besubstituted by one or two C₁ -C₄ alkyl groups, and R⁵ is hydrogen or a--Z--R⁶ group in which R⁶ is phenyl, naphthyl or pyridyl, or is phenyl,naphthyl or pyridyl each of which is substituted by one or twosubstituents from the group halogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₁ -C₄haloalkoxy, C₁ -C₄ haloalkyl, C₁ -C₄ alkylthio, C₁ -C₄ haloalkylthio,di-C₁ -C₄ alkylamino, nitro, cyano, C₁ -C₄ alkoxycarbonyl and C₁ -C₄alkylcarbonyl, and Z is oxygen, sulfur, a direct bond, --NH--, --N(C₁-C₂ alkyl)--, --N(CHO)--, --CH₂ --, --CH(CH₃)-- or --C(CH₃)₂ --. 3.1-(2,6-diisopropyl-4-phenoxyphenyl)-4-isopropyl-5-oxo-2-tetrazolineaccording to claim
 1. 4.1-(2,6-diisopropyl-4-phenoxyphenyl)-5-oxo-2-tetrazoline according toclaim
 2. 5.1-[2,6-diisopropyl-4-(2-chlorophenoxy)-phenyl]-4-isopropyl-5-oxo-2-tetrazolineaccording to claim
 1. 6.1-[2,6-diisopropyl-4-(2-chlorophenoxy)-phenyl]-5-oxo-2-tetrazolineaccording to claim 2.